2003 61 1 22 28 ACTA CHIMICA SINICA Vol 61 2003 No 1 22 28 DNA Ξ Ξ ( 430072) - (MB) DNA DNA DNA DNA MB MB DNA DNA ( ) DNA MB DNA Electrochemical Study on the Interaction of D NA with Several Surfactants ZHAO Fa2Qiong ZENG Bai2Zhao PANG Dai2Wen Ξ ( College of Chemical and Molecular Science Wuhan University Wuhan 430072) Abstract The interaction of DNA with several surfactants was investigated by cyclic voltammetry UV2vis spectrum and ac impendance using MB as the redox probe It was found that all anionic cationic and non2ionic surfactants can bind to DNA immobilized on the electrode surface changing the surface state of DNA thus affects the electrochemical behavior of the probe The interaction between DNA and anionic surfactants is attributed to electrostatic repulsion and hydrophobic binding which makes the peak current of MB decrease Non2ionic surfactants bind to DNA weakly but they can partly change the conformation of surface DNA because they changed the solution properties While cationic surfactants bind to DNA via hydrophobic interaction and electrostatic attraction This interaction is influenced by the length of the hydrophobic carbon chain and the size of the polar headgroup of cationic surfactants Among them cetyltrimethylammonium bromide and dodecyltrimethylammonium chloride can improve the electrochemical response of the probe in certain concentration range while cetylpyridinium bromide and octadecyltrimethylammonium bromide depress the probe s response Keywords DNA surfactant methylene blue gold electrode [7 Bard 8] DNA [1 3] [9 10] [4 6] [11] DNA DNA DNA [12 15] DNA Ξ E2mail : dwpang @whu edu cn Received July 6 2002 ; revised September 15 2002 ; accepted September 25 2002 (Nos 20173040 29773034 20025311)
No 1 : DNA 23 DNA ) 510 mv 10 5 011 Hz 1 1 1 CHI 617A ( ) 273A 2 1 MB 5210 ( EG & G PAR ) 1339 ( ) 5 mmol/ L MB : ( DNA ( 1a) ( E pc ) DNA/ Au) HO2( CH 2 ) 6 2S2S2( CH 2 ) 6 2O ( PO) 3 TGTACA2 GTCATCGGG23 ( HS2ssDNA ) 5 2CCCGATGACTGTACA23 ( ss2 DNA) ( ) ; DNA SDS MB i p 165 g/ ml HS2ssDNA TE (10 mmol/ L ph 810 Tris2HCl + 1 mmol/ L EDTA) 165 g/ ml ssdna TE ( ssdna i pc ) 2 mol/ L NaCl NaCl 015 mol/ MB L 38 2 h MB 2 h 015 mol/ L NaCl 21 mol/ L HS2 MB dsdna (MB ) (DTAC ) (CTAB 98 % BDH ) MB (CPB > 98 % Fluka ) MB (OPB ) ( SDS ) Triton X2100 (Rohm2Haas ) Tween280 ( MB (MB red ) ) Triton X2100 Tween280 1 100 MB i pa MB SDS 1 2 DNA/ Au MB 0105 m Al 2 O 3 MB i pc SDS 015 mol/ L H 2 SO 4 [16] (01047 cm 2 ) 3 L 313 mol/ L HS2ssDNA ( 10 pmol) ( 015 mol/ L NaCl) 2 L 21 mol/ L HS2dsDNA ( 40 pmol) 315 h HS2ssDNA ( ssdna2s/ Au) HS2dsDNA (dsdna2 S/ Au) 113 2 5 mmol/ L ph 619 10 min 5 mol/ L MB - 0130 V ( E pa ) - 0118 V (CTAB DTAC CPB OPB) MB i pa i pc E pa E pc E pc Triton X2100 Tween280 MB 5 10 min 1 MB DNA 015 mmol/ L Figure 1 CVs of 10 mol/ L MB at a bare gold electrode (a) and K 3 Fe ( CN) 6 / 015 mmol/ L K 4 Fe ( CN) 6 0102 5 mol/ L MB at ssdna2s/ Au (b) and dsdna2s/ Au (c) mol/ L (ph 619) Electrolyte : 5 mmol/ L phosphate saline buffer (ph 619) Scan rate : 100 01151 V (Fe (CN) 4 6 - / Fe (CN) 3 6 - mv/ s ; scan direction : negative first
24 Vol 61 2003 MBred i pa SDS i pa 1 E pa E pc E p E p MB - SDS MB 660 nm OPB Tween280 MB MB [17 19] MB [18 19] 2 MB DNA Figure 2 Dependence of peak current of MB on the scan rate MB 2 2 DNA MB (a) dsdna2s/ Au and (b) ssdna2s/ Au 5 mmol/ L phosphate buffer (ph 619) + 5 mol/ L MB other conditions are as in Figure 1 MB MB ssdna 1 b c MB ssdna2s/ Au dsdna2s/ MB dsdna Au MB [6] MB dsdna ssdna2s/ Au i pa i pc 146 % 65 % [20 21] dsdna2s/ Au MB dsdna2s/ Au 223 % 124 % MB DNA MB MB 2 MB MB dsdna i pa i pc MB DNA/ Au 1 ( 2 3 ) ssdna dsdna MB ssdna/ Au SDS MB i p E p E pc dsdna2s/ Au ssdna2s/ Au 1 E pa E f MB ssdna2s/ ssdna Au MB dsdna2s/ Au i p [22] MB SDS E p E pa E pc ssdna2 [19] MB S/ Au E pa E pc MB MB MB DNA DNA MB ssdna2s/ Au E f i p 15 mv dsdna2s/ Au 16 mv DNA DNA MB ssdna dsdna ssdna dsdna [1 3 5 7] ssdna (15 bp dsdna 511 nm) 1 MB Table 1 Electrochemical parameters observed in 5 mmol/ L phosphate buffer (ph 619) containing 10 mol/ L (for bare Au) or 5 mol/ L MB (for DNA2S/ Au) Electrode E pa / V 1 E pc / V 2 i pa / A 3 i pc / A 4 E a f / V 5 E p / V Bare Au - 01177 01011-01291 01015 0147 0106-1151 0117-0124 0101 114 ssdna2s/ Au - 01194 01002-01254 01006 1117 01203-2150 01257-01225 01002 60 dsdna2s/ Au - 01228 01004-01284 01007 1153 01136-3139 0109-01256 01006 56 a E f = ( E pa + E pc ) / 21 The E pa E pc i pa i pc and E f are the mean value of 8 measurements with different electrodes on different day1 from 1 to 5 are the standard deviation of E pa E pc i pa i pc and E f respectively1 Other conditions are as in Figure 11
No 1 : DNA 25 2 ssdna2s/ Au MB Table 2 Electrochemical parameters obtained at ssdna2s/ Au SDS DTAC CTAB CPB OPB Triton X2100 Tween280 c/ ( mol L - 1 ) E pa / V E pc / V i pa / A i pc / A E f / mv E p / mv or V 3 / L 0-0 196-0 257 1 369-2 641 61 5-0 197-0 258 1 367-2 605 1 61 10-0 196-0 257 1 344-2 567 1 61 50-0 198-0 252 1 159-2 167 1 5 54 250-0 199-0 244 0 8902-1 616 5 45 775-0 205-0 239 0 4673-0 8972 4 5 34 0-0 196-0 245 0 7114-2 004 49 5-0 196-0 246 0 7933-2 087-0 5 50 25-0 196-0 247 0 8612-2 129-1 51 100-0 192-0 253 1 278 2 299-2 61 250-0 186-0 247 1 350-2 347 4 61 775-0 163-0 222 1 505-2 175 28 59 0-0 197-0 257 1 090-2 522 60 5-0 191-0 252 1 356-2 517 5 5 61 10-0 180-0 238 1 366-2 083 18 58 50-0 125-0 183 0 6443 0 3639 73 58 100-0 113-0 175 0 5100 0 1999 83 62 250-0 105 0 4770 0-0 190-0 247 1 191-2 232 57 2 5-0 175-0 229 1 129-1 649 16 5 54 5-0 154-0 201 0 7999-0 8919 41 47 25-0 113 0 4325 125-0 097 0 3753 0-0 193-0 261 1 297 2 780 68 5-0 137-0 198 0 6425 0 6167 59 5 61 25-0 090 0 3640 100-0 087 0 3183 0-0 193-0 258 1 296-2 660 65 10-0 191-0 256 1 418-2 636 2 65 20-0 190-0 253 1 518-2 599 4 63 100-0 185-0 247 1 965-2 637 9 5 62 200-0 193-0 255 1 358 2 712 1 5 62 500-0 192-0 255 1 141-2 758 2 63 1000-0 190-0 249 0 859 2 693 6 59 0-0 191-0 256 1 200-2 648 65 10-0 191-0 259 1 326-2 751-1 5 68 50-0 191-0 258 1 381-2 775-1 67 200-0 187-0 252 1 379-2 745 4 65 500-0 178-0 241 1 282-2 645 14 63 1000-0 151-0 215 1 144-2 300 40 5 64 2000-0 040-0 094 1 122-1 407 156 5 54 E f denotes the difference of formal potential in the presence and in the absence of surfactant Other conditions are as in Figure 1 DNA SDS ssdna ssdna 01499 nm [23] SDS SDS ssdna 015 nm 211 nm [24] SDS ssdna SDS ssdna MB SDS SDS ssdna
26 Vol 61 2003 3 dsdna2s/ Au MB Table 3 Electrochemical parameters obtained at dsdna2s/ Au SDS DTAC CTAB CPB OPB Triton X2100 Tween280 c/ ( mol L - 1 ) E pa / V E pc / V i pa / A i pc / A E f / mv E p / mv or V 3 / L 0-0 226-0 276 1 601-3 460 50 5-0 232-0 278 1 752-3 483-4 46 10-0 228-0 274 1 617-3 421 0 46 25-0 222-0 272 1 364-3 199 4 50 50-0 222-0 264 0 9914-2 488 8 42 250-0 222-0 252 0 5309-1 292 14 30 500-0 224-0 258 0 3154-0 8035 10 34 0-0 224-0 274 1 297-3 504 50 10-0 228-0 276 1 819-3 596-3 48 50-0 224-0 276 1 884-3 735-1 52 100-0 216-0 272 2 239-3 679 6 56 250-0 202-0 264 2 744-3 483 17 62 500-0 192-0 242 2 127-2 200 33 50 1000-0 180-0 230 0 7753-0 5517 45 50 0-0 235-0 291 1 499-3 471 56 3 5-0 227-0 283 1 710-3 233 8 56 7-0 216-0 269 1 871 2 744 20 5 53 17 5-0 172-0 213 1 280-0 813 70 5 41 50-0 142-0 204 0 6017-0 2357 90 62 250-0 122-0 218 0 3312-0 0966 93 96 1000-0 114 0 1940 0-0 234-0 294 1 405-3 228 60 2 5-0 226-0 284 1 711-3 034 9 58 5-0 214-0 268 1 841-2 572 23 54 12 5-0 176-0 210 1 104-0 8042 71 34 25-0 152-0 192 0 5643-0 2317 92 40 50-0 142-0 192 0 4398-0 1507 97 50 125-0 134-0 194 0 3639-0 1049 100 60 0-0 224-0 278 1 709-3 301 54 5-0 168-0 212 1 195-0 7395 61 44 10-0 128-0 210 0 4116-0 1268 82 82 25-0 112-0 230 0 3131-0 0779 80 118 125-0 106-0 236 0 2765-0 8138 80 130 0-0 228-0 290 1 673-3 414 62 10-0 228-0 284 1 907-3 473 3 56 50-0 226-0 280 2 395-3 471 6 54 100-0 222-0 278 2 370-3 388 9 56 200-0 224-0 282 1 635-3 635 6 58 1000-0 210-0 270 0 9075-3 497 19 60 0-0 228-0 284 1 503-3 338 56 10-0 228-0 282 1 633-3 539 1 54 50-0 228-0 282 1 576-3 456 1 54 100-0 226-0 278 1 482-3 384 4 52 200-0 222-0 274 1 325-3 235 8 52 500-0 210-0 266 1 066-2 953 18 56 1000-0 188-0 246 0 9287-2 513 39 58 The conditions are as in Table 2
No 1 : DNA 27 3 Fe (CN) - 6 ssdna2 S/ Au Figure 3 Complex plane impedance spectra for 015 mmol/ L K 4 Fe2 (CN) 6 / 015 mmol/ L K 3 Fe (CN) 6 in the absence ( ) or presence of surfactant ( ) (a) 25 50 100 mol/ L SDS ( ) 10 25 50 mol/ L CTAB ( ) and 10 25 50 mol/ L DTAC ( ) ; (b) 215 1215 25 mol/ L CPB ( ) and 5 25 65 mol/ L OPB ( ) from top to bottom1 Electrolyte : 20 mmol/ L phosphate buffer (ph 619) ssdna2s/ Au E f E p 3 ssdna dsdna Fe (CN) - 6 DNA/ Au SDS MB ( ) R ct SDS DNA CPB MB dsdna2 DNA S/ Au i pa ssdna2s/ Au i pc ssdna dsdna dsdna MB dsdna DTAC MB i p CPB i pc CPB DTAC dsdna CPB ssdna ssdna MB red MB dsdna MB i pa CPB DTAC DTAC dsdna MB red DNA MB DNA i pa DTAC MB dsdna2s/ Au i p DTAC MB E p i pa 250 mol/ L ssdna2s/ Au DTAC E p CTAB i pc i pa E p dsdna ssdna DTAC CPB OPB MB dsdna2s/ Au Tween280 i p E p OPB CPB CTAB i p MB i pc CPB MB i p 3 CTAB CPB R ct OPB DNA DNA Rct CPB CTAB DTAC ssdna CPB CTAB ssdna R ct CTAB CPB OPB MB i pc i pa ( 2) ssdna MB ssdna MB red MB MB SDS2MB MB MB Triton X2100 Tween280 MB( ) DNA MB DNA MB [22] i pa i pc E p ; i p E p Tween280 dsdna2s/ Au MB 3 Fe (CN) - 6 DNA ( ) DNA DNA Fe ( CN) - 6 DNA Fe (CN) - 6 MB
28 Vol 61 2003 : DNA 11 Labuda J ; Buckova M ; Jantova S ; Fresenius J Anal ; DNA Chem 2000 367 364 ; DNA 12 Hayakawa K ; Santerre J DNA Chem 1983 17 175 P ; Kwak J C T Biophys 13 Wei W ; Yeung E S Anal Chem 2001 73 1776 [22] DNA DNA 14 Wang L L ; Yoshida J ; Ogata N Chem Mater 2001 13 1273 15 Yoshikawa K Advanced Drug Delivery Reviews 2001 52 235 DNA 16 Angerstein2kozlowska H ; Conway B E ; Hamelin A ; References 1 Cater M T ; Bard A J J Am Chem Soc 1987 109 7528 2 Cater M T ; Rodoriguez M ; Bard A J J Am Chem Soc 1989 111 8901 3 Rodoriguez M ; Bard A J Anal Chem 1990 62 2658 4 Vrana O ; Brabec V Bioelectrochem Bioenerg 1988 19 145 5 Shen H2B ; Kang Y2Z ; Yang H2F ; Yu L ; Zhang Z2 R Chin J Electrochem 1998 4 (4) 400 (in Chinese) ( 1998 4 (4) 400 ) 6 Zhao G2C ; Zhu J 2J ; Zhang J 2J ; Chen H2Y Anal Chim Acta 1999 394 337 7 Pang D W ; Abruna H D Anal Chem 1998 70 3162 8 Pang D W ; Abruna H D Anal Chem 2000 72 47001 9 Labuda J ; Buckova M ; Vanickova M ; Mattusch J ; Wennrich R Electroanal 1999 11 (2) 101 10 Lisdat F ; Ge B ; Krausse B ; Ehrlich A ; Biener H ; Scheller W Electroanal 2001 13 (15) 1225 Stoichviciu L J Electroanal Chem 1987 228 429 17 Ci Y 2X ; Yang L2M Chin Sci Bull 1983 28 (16) 980 (in Chinese) ( 1983 28 (16) 980 ) 18 Zheng Y2X Fenxi Shiyanshi 1984 3 (5) 1 (in Chinese) ( 1984 3 (5) 1 ) 19 He X 2W ; Li H Fenxi Shiyanshi 1985 4 (1) 7 ( in Chinese) ( 1985 4 (1) 7 ) 20 Erdem A ; Kerman K ; Meric B ; Ozsoz M Electroanal 2001 13 (3) 219 21 Kelley S O ; Barton J K Bioconjugate Chem 1997 8 311 22 Li L2S ; Huang W2D ; Wang L2P ; Yan Y Acta Chim Sinica 2002 60 (1) 98 (in Chinese) ( 2002 60 (1) 98 ) 23 Whitesides P E ; Laibins P E Langmuir 1990 6 87 24 Zhao G2X Physical Chemistry of Surfactants Peking University Press Beijing 1991 p 77 (in Chinese) ( 1991 p 77 ) (A0206065 SHEN H )